CN111883642B - Cu 2-x S-based thermoelectric material and solvothermal preparation method - Google Patents
Cu 2-x S-based thermoelectric material and solvothermal preparation method Download PDFInfo
- Publication number
- CN111883642B CN111883642B CN202010785187.6A CN202010785187A CN111883642B CN 111883642 B CN111883642 B CN 111883642B CN 202010785187 A CN202010785187 A CN 202010785187A CN 111883642 B CN111883642 B CN 111883642B
- Authority
- CN
- China
- Prior art keywords
- thermoelectric material
- reaction
- based thermoelectric
- cucl
- solvothermal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/01—Manufacture or treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/12—Sulfides
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/80—Constructional details
- H10N10/85—Thermoelectric active materials
- H10N10/851—Thermoelectric active materials comprising inorganic compositions
- H10N10/852—Thermoelectric active materials comprising inorganic compositions comprising tellurium, selenium or sulfur
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
Abstract
The invention relates to Cu 2‑x The S-based thermoelectric material and the solvothermal preparation method comprise S1 reaction of Na 2 S·9H 2 Adding O into a p-polyphenyl or polytetrafluoroethylene reaction tank filled with ethylene glycol, and fully stirring until the O is dissolved; s2 according to CuCl and Na 2 S·9H 2 Adding CuCl into the solution in S1 according to the molar ratio of O being 2: 1-1.7: 1, and mixing uniformly; s3, sealing the reaction tank, and then filling the reaction tank into a solvent-heating steel outer tank; s4, heating the sealed solvent thermal reaction kettle in a drying box for reaction to obtain a sample; s5, cleaning and centrifugally collecting the sample obtained in the step S4, and drying the sample at 40-80 ℃ for 2-24 hours in vacuum; s6 preparation of Cu from S5 2‑x Sintering the S-based nano powder into a block to obtain Cu 2‑x An S-based thermoelectric material. The method adopts a solvothermal method, adopts salts of Cu and S as precursors, has low synthesis temperature and simple and convenient operation, and can be prepared in large quantities.
Description
Technical Field
The invention belongs to the field of thermoelectric energy conversion materials, and particularly relates to Cu 2-x An S-based thermoelectric material and a solvothermal preparation method.
Background
The thermoelectric material is an energy conversion material capable of realizing direct and mutual conversion between heat energy and electric energy, has a wide application prospect in the fields of waste heat recovery power generation, thermoelectric refrigeration and the like, and has recently received extensive attention and research in academia and industry. The important index for measuring the thermoelectric energy conversion efficiency of the material is the dimensionless thermoelectric figure of merit,ZT = S 2 σT/κwhereinSIs the coefficient of the Seebeck, and,σis the electrical conductivity of the water to be treated,Tis the temperature of the liquid to be measured in absolute terms,κis the thermal conductivity. The high-performance thermoelectric material is required to have an excellent power factor: (S 2 σ) And low thermal conductivity. On the one hand, thermoelectric researchers are going to improve the thermoelectric performance of classical thermoelectric materials (e.g., making nanostructures, enhancing phonon scattering, thereby achieving low thermal conductivity), and on the other hand, are going to develop new intrinsic high performance thermoelectric materials.
In recent years, Cu 2 S-based liquid materials have received much attention in the thermoelectric field due to low toxicity, high storage capacity, and low thermal conductivity. Studies have shown that in Cu 2 Introduction of Cu vacancy into S (i.e. formation of Cu) 2-x S), the power factor can be greatly improved, and 1000K is achievedZTValue from 0.7Lifting to 1.7. At present, Cu is prepared 2-x The methods of S thermoelectric materials are mainly high temperature melting and ball milling methods, both of which require high purity, high cost elemental raw materials and cannot control the microscopic morphology of the nano-scale. To promote Cu 2- x In the thermoelectric application of S-based materials, a controllable synthesis method which has low preparation temperature, low cost, no need of high-purity simple substance raw materials and can effectively control the nanometer morphology needs to be developed.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides Cu 2-x An S-based thermoelectric material and a solvothermal preparation method.
In order to solve the technical problems, the invention adopts the following technical scheme: cu 2-x The solvothermal preparation method of the S-based thermoelectric material comprises the following steps:
s1 adding Na 2 S·9H 2 Adding O into a reaction tank filled with ethylene glycol and p-polyphenyl or polytetrafluoroethylene, and fully stirring until the mixture is Na 2 S·9H 2 Dissolving O;
s2 according to CuCl and Na 2 S·9H 2 The molar ratio of O to Na in S1 is 2:1 to 1.7:1 2 Adding CuCl into the S glycol solution, and fully and uniformly mixing;
s3, sealing the p-polyphenyl or polytetrafluoroethylene reaction tank, and then filling the reaction tank into a solvent-heating steel outer tank;
s4, placing the sealed solvent thermal reaction kettle in a drying box at room temperature, heating the drying box to a reaction temperature, and reacting to obtain a sample, wherein the reaction temperature is 180-230 ℃, and the reaction time is 1-48 h;
s5, cleaning and centrifugally collecting the sample obtained in the step S4, and drying the sample in vacuum at 40-80 ℃ for 2-24 hours;
s6 hot pressing and sintering the Cu obtained in S5 2-x Sintering the S-based nano powder into a block to obtain Cu 2-x The S-based thermoelectric material is sintered at the temperature of 500-600 ℃ for 10-60 min.
As an improvement, the CuCl and Na in the S2 2 S·9H 2 The molar ratio of O is 2: 1.
As an improvement, the CuCl and Na in the S2 2 S·9H 2 The molar ratio of O is 1.9: 1.
As an improvement, the CuCl and Na in the S2 2 S·9H 2 The molar ratio of O is 1.8: 1.
As an improvement, the CuCl and Na in the S2 2 S·9H 2 The molar ratio of O is 1.7: 1.
As an improvement, the reaction temperature in the step S4 is 220 ℃, and the reaction time is 24 h.
Cu 2-x S-based thermoelectric material and Cu prepared by adopting solvothermal preparation method 2-x An S-based thermoelectric material.
Compared with the prior art, the invention has at least the following advantages:
1. the invention adopts the solvothermal method, adopts salts of Cu and S as precursors, has low synthesis temperature, simple and convenient operation, can be prepared massively, does not need high-purity Cu and S simple substances in preparation, has lower temperature than the commonly adopted high-temperature melting-annealing process, and has short preparation time.
2. The invention can obtain Cu 2-x The S hollow sphere is composed of nano particles, can better control the nanoscale morphology compared with a ball milling method, and does not depend on special ball mill equipment.
3. The invention takes ethylene glycol as solvent, does not need to adopt S simple substance, and avoids the potential danger of inflammable and fire; long-chain organic solvent is not used, so that adverse effects on the thermoelectric performance of the product are avoided; by simply regulating and controlling CuCl/Na in the precursor 2 The proportion of S realizes the optimization and promotion of the thermoelectric performance of the product.
Drawings
FIG. 1 shows Cu in different stoichiometric ratios 2-x XRD pattern of S, (a) is Cu 2-x XRD pattern of S powder, (b) XRD pattern of bulk, with abscissa 2theta (degree) representing diffraction angle (degrees) and Intensity (a.u.) representing Intensity (no units).
FIG. 2 is a graph of Cu at a stoichiometric ratio of 1.7:1 2-x SEM image of S, (a) is Cu 2-x SEM image of S powder, and (b) SEM image of bulk.
FIG. 3 is a graph of Cu at stoichiometric ratios of 2:1, 1.9:1, and 1.8:1 2-x The ordinate of the S thermoelectric performance diagram (a) to (f) represents the electrical conductivity, the Seebeck coefficient, the power factor, the thermal conductivity, the lattice thermal conductivity and the thermoelectric figure of merit respectively, and the abscissa is the temperature and the temperature unit is Kelvin.
FIG. 4 is a flow chart of the method of the present invention.
Detailed Description
The present invention is described in further detail below.
The technical scheme of the invention aims to controllably prepare Cu with different vacancy concentrations by using a low-temperature and low-cost solvothermal method 2-x The S-based thermoelectric material aims to solve the problems of preparation and performance optimization of the material: (1) preparation of Cu by the prior art 2-x The S thermoelectric material mainly adopts a high-temperature melting method, needs high preparation temperature and long reaction time, and needs high-purity elementary substance raw materials; the method of the invention adopts the compound, thus reducing the requirements on raw materials. In addition, most of the copper-sulfur thermoelectric materials are prepared by a solid-phase method, the raw materials required to be used are high-purity simple substances, and the invention adopts a solvothermal method which is a chemical method, so that chemical reaction can be carried out by using compounds; (2) preparation of Cu by the prior art 2-x The mechanical ball milling method used by S thermoelectric material is difficult to control the nano-morphology, and high-purity simple substance raw material is also needed, but the invention adopts the solution chemical reaction method to obtain Cu 2-x The nano-morphology of the S-based thermoelectric material is controllable, and the reaction mechanism of the invention is 2CuCl + Na 2 S = Cu 2 S ↓ +2NaCl can realize the control of the nanometer shape through the regulation and control of the crystal nucleation and growth; (3) preparation of Cu by the prior art 2- x The solution method used by S thermoelectric material needs to use S powder as a precursor (with flammable risk), or adopts a long-chain organic solvent which is difficult to clean as a solvent (having potential negative influence on thermoelectric performance), or can not generate Cu vacancy which can be regulated and controlled + Stabilized in ethylene glycol when usedA molar ratio of starting materials below 2:1 results in a controlled Cu vacancy concentration during the reaction.
In order to solve the technical problems, the technical scheme of the invention aims to realize high-performance Cu by a solvothermal method 2-x And (S) controllable preparation of the nano material. The scheme adopts ethylene glycol as a reaction solvent and CuCl and Na 2 S·9H 2 O is used as a precursor, a high-purity simple substance raw material and a long-chain organic solvent are not needed, and Cu can be realized at a lower temperature (180 ℃ plus 230 ℃) 2-x Preparing an S-based thermoelectric material; by regulating and controlling CuCl/Na in the precursor 2 The proportion of S realizes the optimization and promotion of thermoelectric performance.
Referring to fig. 1-4: cu 2-x The solvothermal preparation method of the S-based thermoelectric material comprises the following steps:
s1 adding Na 2 S·9H 2 Adding O into p-polyphenyl or polytetrafluoroethylene reaction tank filled with glycol, and fully stirring until Na is obtained 2 S·9H 2 And dissolving the O.
S2 according to CuCl and Na 2 S·9H 2 The molar ratio of O is 2: 1-1.7: 1, Na is added into S1 2 Adding CuCl into the S ethylene glycol solution, and fully and uniformly mixing.
And S3, sealing the p-polyphenyl or polytetrafluoroethylene reaction tank, and then filling the reaction tank into a solvent-heated steel outer tank.
S4, placing the sealed solvent thermal reaction kettle in a drying box at room temperature, heating the drying box to a reaction temperature, and reacting to obtain a sample, wherein the reaction temperature is 180-230 ℃ and the reaction time is 1-48 h; in specific implementation, the reaction temperature can be 180 ℃, 190 ℃, 200 ℃, 210 ℃, 220 ℃ or 230 ℃, and the reaction time can be 1h, 5h, 12h, 18h, 20h, 24h, 28h, 30h, 36h, 40h, 45h or 48 h; the reaction temperature is preferably 220 ℃, and the reaction time is preferably 24 h. And (3) placing the sealed solvent thermal reaction kettle in a drying box, heating to the reaction temperature of 220 ℃ from room temperature, reacting for 24 hours, and then cooling to room temperature.
And S5, cleaning and centrifugally collecting the sample obtained in the step S4, and drying the sample in vacuum at 40-80 ℃ for 2-24 hours. In the specific implementation, the drying temperature can be selected from 40 ℃, 50 ℃, 60 ℃, 70 ℃ or 80 ℃; the drying time can be 2h, 5h, 10h, 12h, 15h, 18h, 20h or 24 h.
S6, hot-pressing and sintering the Cu obtained in S5 2-x Sintering the S-based nano powder into a block to obtain Cu 2-x The S-based thermoelectric material is sintered at the temperature of 500-600 ℃ for 10-60 min. In specific implementation, the sintering time can be 500 ℃, 520 ℃, 550 ℃, 580 ℃ or 600 ℃, the sintering time can be 10min, 20min, 30min, 40min, 50min or 60min, the sintering temperature is preferably 550 ℃, and the sintering time is preferably 20 min. The sintering process is carried out at a temperature that is raised from room temperature to the sintering temperature.
The reaction time in all steps was timed after the corresponding reaction temperature was raised.
Example 1: cu when the ratio of precursor Cu/S is 2:1 2-x The preparation process of the S-based thermoelectric material comprises the following steps:
1) weighing 8 mmol of Na 2 S·9H 2 Adding O into a p-polyphenyl or polytetrafluoroethylene reaction tank filled with 60 ml of ethylene glycol, and fully stirring until the mixture is Na 2 S·9H 2 Dissolving O;
2) weigh 4 mmol of CuCl and add to Na 2 Stirring the solution of S in glycol for 30min at normal temperature;
3) sealing the p-polyphenyl or polytetrafluoroethylene reaction tank, and then filling the reaction tank into a solvent-heating steel outer tank;
4) placing the sealed solvent thermal reaction kettle in a drying box at 220 ℃, reacting for 24 hours, and cooling to room temperature;
5) washing and centrifugally collecting a sample, and performing vacuum drying at 60 ℃ for 12 hours;
6) hot-pressing and sintering to obtain Cu 2-x Sintering the S-based nano powder at 550 ℃ for 20min to form a block, thus obtaining Cu 2-x An S-based thermoelectric material.
Example 2: cu when the Cu/S ratio of the precursor is 1.9:1 2-x The preparation process of the S-based thermoelectric material comprises the following steps:
1) 7.6 mmol of Na are weighed 2 S·9H 2 Adding O into p-polyphenyl or polytetrafluoroethylene containing 60 ml ethylene glycol for reactionIn a pot, fully stirring until Na 2 S·9H 2 Dissolving O;
2) weigh 4 mmol of CuCl and add to Na 2 Stirring the solution of S in glycol for 30min at normal temperature;
3) sealing the p-polyphenyl or polytetrafluoroethylene reaction tank, and then filling the reaction tank into a solvent-heating steel outer tank;
4) placing the sealed solvent thermal reaction kettle in a drying box at the temperature of 220 ℃, reacting for 24 hours, and cooling to room temperature;
5) washing and centrifugally collecting a sample, and performing vacuum drying at 60 ℃ for 12 hours;
6) hot-pressing and sintering to obtain Cu 2-x Sintering the S-based nano powder at 550 ℃ for 20min to form a block, thus obtaining Cu 2-x An S-based thermoelectric material.
Example 3: cu when the Cu/S ratio of the precursor is 1.8:1 2-x The preparation process of the S-based thermoelectric material comprises the following steps:
1) weighing 7.2 mmol of Na 2 S·9H 2 Adding O into a p-polyphenyl or polytetrafluoroethylene reaction tank filled with 60 ml of ethylene glycol, and fully stirring until the mixture is Na 2 S·9H 2 Dissolving O;
2) weigh 4 mmol of CuCl and add to Na 2 Stirring the solution of S in glycol for 30min at normal temperature;
3) sealing the p-polyphenyl or polytetrafluoroethylene reaction tank, and then filling the reaction tank into a solvent-heating steel outer tank;
4) placing the sealed solvent thermal reaction kettle in a drying box at 220 ℃, reacting for 24 hours, and cooling to room temperature;
5) washing and centrifugally collecting a sample, and performing vacuum drying at 60 ℃ for 12 hours;
6) hot-pressing and sintering to obtain Cu 2-x Sintering the S-based nano powder at 550 ℃ for 20min to form a block, thus obtaining Cu 2-x An S-based thermoelectric material.
Example 4: cu when the Cu/S ratio of the precursor is 1.7:1 2-x The preparation process of the S-based thermoelectric material comprises the following steps:
1) 6.8 mmol of Na are weighed 2 S·9H 2 O to a p-polyparaphenylene containing 60 ml of ethylene glycolOr in a polytetrafluoroethylene reaction tank, fully stirring until the mixture is Na 2 S·9H 2 Dissolving O;
2) weigh 4 mmol of CuCl and add to Na 2 Stirring the solution of S in glycol for 30min at normal temperature;
3) sealing the p-polyphenyl or polytetrafluoroethylene reaction tank, and then filling the reaction tank into a solvent-heating steel outer tank;
4) placing the sealed solvent thermal reaction kettle in a drying box at 220 ℃, reacting for 24 hours, and cooling to room temperature;
5) washing and centrifugally collecting a sample, and performing vacuum drying at 60 ℃ for 12 hours;
6) hot-pressing and sintering to obtain Cu 2-x Sintering the S-based nano powder at 550 ℃ for 20min to form a block, thus obtaining Cu 2-x An S-based thermoelectric material.
In fig. 1, (a) and (b) represent XRD patterns of the powder after reaction and the bulk after sintering, respectively, indicating the phase composition of the substance. The results show that the solvothermal product is single-phase Cu at a precursor Cu/S ratio of 2:1 2 S; when the precursor ratio is reduced to 1.9:1 and 1.8:1, the solvothermal product is Cu 2 S and Cu 1.96 A complex of S.
In fig. 2, (a) and (b) represent SEM images of the solvothermal synthesized powder and sintered mass with a precursor Cu/S ratio of 1.7:1, respectively, depicting their micro-morphologies. Wherein the micro-morphology of the powder is a hollow sphere composed of micron sheets, and the sintered block is composed of submicron particles and has pores.
In fig. 3, (a) represents the electric conductivity, (b) is the Seebeck coefficient, (c) is the power factor, (d) is the total thermal conductivity, (e) is the lattice thermal conductivity, and (f) represents the thermoelectric figure of merit. When the ratio of the precursor Cu/S is reduced from 2:1 to 1.8:1, the electrical conductivity (shown in a figure (a)) and the power factor (shown in a figure (c)) of the corresponding sintered block can be remarkably improved, and lower lattice thermal conductivity (shown in a figure (e)) can still be maintained, and finally, the great improvement of the thermoelectric figure of merit of the thermoelectric performance of the evaluation material is realized, as shown in a figure (f).
Finally, the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting, although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all of them should be covered in the claims of the present invention.
Claims (5)
1. Cu 2-x The solvothermal preparation method of the S-based thermoelectric material is characterized by comprising the following steps of: the method comprises the following steps:
s1 adding Na 2 S·9H 2 Adding O into p-polyphenyl or polytetrafluoroethylene reaction tank filled with glycol, and fully stirring until Na is obtained 2 S·9H 2 Dissolving O;
s2 according to CuCl and Na 2 S·9H 2 A molar ratio of O to Na in S1 of 1.9:1 to 1.8:1 2 Adding CuCl into the S glycol solution, and fully and uniformly mixing;
s3, sealing the p-polyphenyl or polytetrafluoroethylene reaction tank, and then filling the reaction tank into a solvent-heating steel outer tank;
s4, placing the sealed solvent thermal reaction kettle in a drying box at room temperature, heating the drying box to a reaction temperature, and reacting to obtain a sample, wherein the reaction temperature is 180-230 ℃ and the reaction time is 1-48 h;
s5, cleaning and centrifugally collecting the sample obtained in the step S4, and drying the sample in vacuum at 40-80 ℃ for 2-24 hours;
s6 hot pressing and sintering the Cu obtained in S5 2-x Sintering the S-based nano powder into a block to obtain Cu 2-x The S-based thermoelectric material is sintered at the temperature of 500-580 ℃ for 10-60 min.
2. Cu according to claim 1 2-x The solvothermal preparation method of the S-based thermoelectric material is characterized by comprising the following steps of: CuCl and Na in S2 2 S·9H 2 The molar ratio of O is 1.9: 1.
3. A Cu as claimed in claim 1 2-x S-based thermoelectricThe solvothermal preparation method of the material is characterized by comprising the following steps: CuCl and Na in S2 2 S·9H 2 The molar ratio of O is 1.8: 1.
4. Cu as claimed in any one of claims 1 to 3 2-x The solvothermal preparation method of the S-based thermoelectric material is characterized by comprising the following steps of: the reaction temperature in the step S4 is 220 ℃, and the reaction time is 24 h.
5. Cu 2-x An S-based thermoelectric material, characterized in that Cu produced by the solvothermal production method according to claim 4 2-x An S-based thermoelectric material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010785187.6A CN111883642B (en) | 2020-08-06 | 2020-08-06 | Cu 2-x S-based thermoelectric material and solvothermal preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010785187.6A CN111883642B (en) | 2020-08-06 | 2020-08-06 | Cu 2-x S-based thermoelectric material and solvothermal preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111883642A CN111883642A (en) | 2020-11-03 |
| CN111883642B true CN111883642B (en) | 2022-08-16 |
Family
ID=73210913
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010785187.6A Active CN111883642B (en) | 2020-08-06 | 2020-08-06 | Cu 2-x S-based thermoelectric material and solvothermal preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111883642B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116081678A (en) * | 2022-12-03 | 2023-05-09 | 昆明理工大学 | Tubular furnace sintering preparation Cu 2 S thermoelectric material method |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102502775A (en) * | 2011-11-23 | 2012-06-20 | 陕西科技大学 | Preparation method of spherical copper sulphide (CuS) particles |
| CN103872237B (en) * | 2012-12-07 | 2017-02-08 | 中国科学院上海硅酸盐研究所 | Copper-sulfur-based high-performance thermoelectric material and preparation method thereof |
| CN104810465B (en) * | 2015-04-21 | 2017-05-17 | 电子科技大学 | Cu2-xS thermoelectric material preparation method |
| JP2018521943A (en) * | 2015-06-01 | 2018-08-09 | 宝山鋼鉄股▲ふん▼有限公司Ｂａｏｓｈａｎ Ｉｒｏｎ ＆ Ｓｔｅｅｌ Ｃｏ．，Ｌｔｄ． | Method for preparing metal chalcogenide nanomaterials |
| CN110980795A (en) * | 2019-11-20 | 2020-04-10 | 江苏大学 | Hydrothermal method for preparing Cu2-xMethod for preparing S nanoflower and application of S nanoflower to near-infrared photothermal material |
| CN111286037B (en) * | 2020-03-03 | 2021-05-28 | 西安交通大学 | Preparation method of morphology-controllable low-dimensional copper-based conjugated polymer nano thermoelectric material |
-
2020
- 2020-08-06 CN CN202010785187.6A patent/CN111883642B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN111883642A (en) | 2020-11-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Xiao et al. | Solar thermal energy storage based on sodium acetate trihydrate phase change hydrogels with excellent light-to-thermal conversion performance | |
| Lan et al. | Morphology-controlled hydrothermal synthesis and growth mechanism of microcrystal Cu2O | |
| WO2022032743A1 (en) | Cote2/mxene composite material and preparation method therefor | |
| CN100402424C (en) | Synthesis method of nano hexaboride | |
| WO2020147288A1 (en) | Composite nanomaterial containing selenium-doped mxene and preparation method and use thereof | |
| Tan et al. | Colloidal syntheses of zero-dimensional Cs 4 SnX 6 (X= Br, I) nanocrystals with high emission efficiencies | |
| Reny et al. | High pressure synthesis of an iodine doped silicon clathrate compound | |
| Yamanaka et al. | Preparation of barium-containing silicon clathrate compound | |
| Qiao et al. | Thermal performance analysis of a thermal enhanced form-stable composite phase change material with aluminum nitride | |
| CN111883642B (en) | Cu 2-x S-based thermoelectric material and solvothermal preparation method | |
| Han et al. | Topotactic anion-exchange in thermoelectric nanostructured layered tin chalcogenides with reduced selenium content | |
| CN102249289A (en) | Method for preparing spiauterite ZnS fine nanorod with solvothermal method | |
| CN111533093A (en) | Preparation method of blocky boron nitride aerogel based on combination of freeze drying method and tubular furnace high-temperature heating method | |
| CN106299392B (en) | Nano Mn with manganese defect3O4Preparation method and application thereof | |
| CN113372012A (en) | Metal element doped inorganic lead-free CsSnI3Method for perovskite stabilization | |
| CN1384048A (en) | Nano level metal telluride preparing process | |
| CN111137923A (en) | Preparation method of prismatic tantalum oxide nano material | |
| Jiang et al. | Preparation and characterization of CuInS2 nanorods and nanotubes from an elemental solvothermal reaction | |
| CN102703160B (en) | Preparation method of graphite-bi-selenylation niobium nanocomposite | |
| CN101759162B (en) | Low-temperature liquid phase synthesizing method of monodisperse square crystalline phase ferrous selenide square nanometer sheet | |
| CN113501969A (en) | Thorium-based metal organic framework material and preparation method and application thereof | |
| CN110240126B (en) | Tin diselenide with nanoflower structure and preparation method thereof | |
| CN110711599A (en) | g-C3N4/Bi5O7I composite microsphere material and preparation method thereof | |
| CN112850649B (en) | Preparation method of bismuth oxybromide nanosheet | |
| CN108821771B (en) | Preparation method of silver-selenium ternary compound polycrystalline block material with high thermoelectric performance |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |